Azoic dye composition containing oxygen-containing primary amines and process of using same

ABSTRACT

A process for the neutral developing of azoic colors and a dye composition which employs said process, which process comprises the use of an oxygen-containing primary amine in combination with coupling components and diazo amino compounds.

United States Patent Inventor Clemens Slreck [50] Field of Search 8/45Loudonvllle, N.Y. APPL 753,744 56] Relerences Clted Filed Aug. 19, 1968UNITED STATES PATENTS a e 212 1971 2,232,405 2/1941 Schmelzer 8/45 Mp0"on Primary Examiner-George F. Lesmes New Y II N.Y.

or Assistant Examiner- Patricia C. Ives H Artorneyswalter C. Kehm andSamson B. Leavitt AZOIC DYE COMPOSITION CONTAINING A OXYGEN-CONTAININGPRIMARY AMINESAND -i PROCESS OF USING SAME ABSTRACT: A process for theneutral developing of azoic MCMmSNO Drawings colors and a dyecomposition which employs said process, US. Cl 8/45, which processcomprises the use of an oxygen-containing pri- V 8/46 mary amine incombination with coupling components and int. Cl D06p 1/02 .diazo aminocompounds.

This invention relates to an improved process for neutral developing ofazoic colors and to the compositions used therein.

More specifically, this invention relates to an improved process forneutral developing of azoic colors wherein the dyeing or printingcomposition contains a sulfonated long chain carboxylic acid and a watersoluble nitrogenous oxygencontaining organic base.

Prior art processes for developing azoic compositions may be broadlyclassified into acidic developing and neutral developing.

ln acidic-developing the diazo compound and the coupling component aredissolved in a caustic alkali solution. The solution is thereafter madeinto a suitable paste by the addition of a thickening agent such asstarch or gum tragacanth. After the paste is applied to the textile, asby printing, thedye is developed byexposing the textile to acidic steam.The acidic steam operates to split the diazo moiety, and the thus freeddiazo couples with the coupling component to produce the color.Generally, acetic acid is used as the acid component in the steam. Whileacidic developing produces the desired dyed effect, attendant therewithare several disadvantages, primary of which is the offensive smell andirritating effect of the acid in the steam vapors. Consequently, priorart workers have attempted to utilize aneutral steam developing process,thereby excluding the use ofany acid.

Various processes for the neutral developing of azoic dyes have beenutilized by prior art workers. The 'basic approach has been the use ofan-alkaline base which, after printing, evaporates on exposure toneutral steam, thereby lowering the pH and enabling the diazo to splitand couple with the coupling component and subsequently produce thecolor. These processes include the addition to the dye preparation oforganic acids, phosphoric acid and salts of acidsas shown in U.S. Pat.No. l,95l,57l;the use of amine salts and amides-in the print compositionas illustrated in U.S. Pat. No. 2,008,966; the replacement of causticalkali by a volatile amine, such as diethylamine, as taught by U.S. Pat.No. 2,125,087; and-the use of an oxygen containing water-solublenitrogenous organic base, e.g. oxygen containing secand tert-aminocompounds, such as diethylaminoethanol or diethylaminoethanol methylether, disclosed in U.S. Pat. No. 2,232,405.

All of the neutral developing techniques described above suffer fromseveral disadvantages. None of the methods, for example, aresatisfactory for use with slow splitting diazo compounds, such as-chloro-o-toluidine diazo stabilized with sarcosine, andS-chloro-o-anisidine diazo stabilized with sarcosine. Furthermore, theshades are duller than when the same dyestuff components are developedin acid steam. The

duller shades are attributable to the necessity of using a highermoisture content in neutral developing than in acidic developing andalso because the dissociation of the diazo compound occurs at acomparatively higher pH in neutral developing than in acidic developing.

it has been found in accordance with the present invention that, byusing 'a printing or dyeing composition containing a water solubleprimary amine having a total of three to five carbon atoms and theformula R-O,-(Cl-l, ),,-NH wherein R is an alkyl of one to four carbonatoms and n is an integer having the value of from 2 to 4 and alsopreferably a sulfonated long chain carboxylic acid, the disadvantages ofthe prior art neutral developing process may be overcome.

Accordingly, it is an object of this invention to provide a novelneutral developing azo dye composition and process for using the same.

Another object of this invention is to provide a neutral developing azodye composition and process which is remarkably effective in cleavingslow-splitting diazo compounds.

A further object of this invention is to provide a neutral developingazo dye composition and process wherein the :colors developed are asconsistently as bright as that produced in the conventional acidicdeveloping composition and .process.

These and other objects are accomplished by a-composition containing avolatile water-soluble ether of an oxygen containing primary amine andalso preferably a sulfonated long-chain carboxylic acid.

These and other objects of the instant invention will be evident fromthe following more detailed description thereof.

We have found that oxygen-containing primary amines which have thegeneral formula:

wherein R represents an alkyl radical having from 1-4 carbon atoms suchas methyl, ethyl, propyl, butyl, isopropyl, isobutyl,

amines previously employed in the art. The primary amines of the instantinvention are more highly volatile than theoxygencontaining secondaryand tertiary amines and in addition have a greater solvent effect on theazoic solutions orpastes. Furthermore, the pad liquors of the instantinvention remain more fluid than those in which oxygen-containing basesemployed in the prior art are used. Amines which may be employed inconnection with the instant invention include, but are not limited to,amines such as methoxyethylamine, methoxypropylamine,methoxybutylamine,ethoxyeth-ylamine, ethoxypropylamine,methoxybutylamine, propoxyethylamine, and any otheramine which conformswith the abovejgeneral formula. The preferred amine for usein theinstant invention is one which has a volatility such that it.givesexcellent color results under the usual conditions employed in theneutral developing of azoic colors. While all theamines listed are useful in connection with the instant invention, the preferred amine ismethoxypropylarnine.

in addition tothe use of the primary amine in the neutral developing ofazoic colors, but not necessary therefor, we have also found that if oneincorporatesa sulfonated longchain carboxylic-acid one obtains acloser'control and an improved time factor in the operation of theinstant invention.

The sulfonated long-chain carboxylic acids are preferably the C to Csulfonated alkyl carboxylic acids such as 'a-sulfolauric acid,a-sulfotridecoic acid, a-sulfomyr'istic acid, asulfopentadecanoic'acid,a-sulfopalmitic acid, a-sulfomargaric acid, and a-sulfostearic acid. Inaddition to the a-sulfonated carboxylic acids disclosed above, the termsulfonated longchain carboxylic acids having from 12 to 18 carbon atomsis intended to include those compounds having one or more substitutedsulfonated groups on any of the carbon atoms such as, for example the B,u, 8", etc., position. The choice of acid and the position and number ofsulfonated groups are dependent, forthe most part, on prevailingeconomic considerations and the availability of the particular acidutilized.

The preferred method of carrying out the instant invention is to preparea solution containing approximately equivalent amounts of a diazo aminocompound and a coupling compound in water and a solvent system. When thevolatile amine of the instant invention is employed it is not usuallynecessary to add any fixed alkali so as to obtain a solution since thevolatile amine has a relatively high solvent power. However, a smallamount of fixed alkali may be employed if desired. The amine may beemployed in amounts of from about 5 to 50 percent based upon the welghtof the solution. If a long-chain sulfonated acid is employed it may alsobe added to the solution in an amount of from 0 to 20 percent based onthe weight of the solution. Furthermore, other adjuvants such as urea,surfactants and thickening agents may be employed. The useful thickeningagents include, but are not limited to, starch, tragacanth, caltax gum,etherified starch, or other similar thickeners. The order in which thecomponents are added to the solution is immaterial to the operationofthe instant invention.

Diazotizable amines useful in connection with the instant invention arethose which are useful in the production of azoic colors. These aminesare free from water-solubilizing sulfonic and carboxylic acid groups andinclude, but are not limited to:

2-methoxy-naphthylamine Z-methoxy-aniline Z-phenoxy-aniline2-ethoxy-aniline 2-chlor-5-methyl-aniline 2-methyl-aniline2-methoxy-5-methyl-aniline 2-methoxy-4-chlor-5-methyl-aniline2:5-dimethoxy-aniline 2:5-diethoxy-aniline 2:5-dimethoxy-4-chlor-aniline-brom-2-methoxy-aniline 3-iodo-6-methoxy-aniline 3-iodo-6-ethoxy-aniline3-methyl-4-chlor-aniline 3-brom-6-ethoxy-aniline3-chlor-6-ethoxy-aniline 3-ethoxy-aniline 3-phenoxy-aniline3-methoxy-aniline 3-brom-6-phenoxy-aniline 3-iodo-6-phenoxy-aniline3-brom-6-methyl-aniline 3-chlor-6-methyl-aniline 3-methyl-aniline3-brom-5-methyl-aniline 3-chlor-6-phenoxy-aniline2:5-dimethyl-4-chlor-aniline 4-ethyl-aniline 4-benzo-trifluor-aniline4-chlor-2methoxy-aniline 4-brom-2-methoxy-aniline4-brom-2-ethoxy-aniline 4-iodo-2-methoxy-aniline 4-meth0xy-aniline4-chlor-2-ethoxy-aniline 4-phenoxy-aniline 4-ethoxy-aniline4-brom-2-phenoxy-aniline 4-methoxy-2-chlor-aniline4-chlor-2-methyl-aniline 4-chlor-2-methyl-aniline4-methyl-3-brom-aniline 4-brom-5-methyl-aniline 4-methyl-2chlor-aniline4-methyl-aniline 4-chlor-2:S-dimethyl-aniline 4-chlor-2-phenoxy-aniline4-methoxy-Z-chlor-aniline 4-phenoxy-2chlor-aniline4-chlor-2:S-diethoxy-aniline 3-chlor-2-methyl-aniline3-chlor-2-methoxy-aniline alpha-naphthylamine beta-naphthylamine Theabove amines are diazotized in the usual manner and their diazocompounds ares stabilized in the manner described in Lubs-The Chemistryof Synthetic Dyes and Pigments pp. 217-221; Rheinhold, NY. 1955, withamines which have at least one solubilizing group to thereby form astabilized diazoamino compound or triazene. Such stabilizing amines aredisclosed in Lubs and may be exemplified by, but not limited to:

ethylamino-acetic acid dibenzylamine-disulfonic acid4-sulfo-2-aminobenzoic acid 5-sulfo-2-aminobenzoic acidl-aminobenzene-2:S-disulfonic acidl-methyl-2-ethyl-aminobenzene-4-sulfonic acid4-amino-5-methylbenzene-2-sulfanilide l-aminonaphthalene-2:4-disulfonicacid l-aminobenzene-2:3-dicarboxylic acid methylamino-ethane-sulfonicacid l-methylaminobenzene-4-sulfonic acid butylamino-acetic acidcyclohexylamino-acetic acid 2-ethylamino-l-methylbenzene-4-sulfonic acidl-aminobenzene-3:5-dicarboxylic acid 3-amin0benzenel :2-dicarboxylicacid 2-methylamino-4-sulfobenzoic acid ethyl-glucaminecyclohexyl-glucamine benzyl-xylamine methyl-erythramineethyl-galactamine amyl-arabinamine methyl-mannamine glycinepiperidine-a-carboxylic acid pyrrolidine-a-carboxylic acidguanylurea-N-sulfonic acid guanyltaurine guanylglycine guanylsulfanilicacid diethyloldicyandiamine sulfocarboxyquinoline cyanamid Couplingcomponents which are useful in connection with the instant invention maybe exemplified by, but are not limited to:

3-hydroxy-2-naphthanilide 3-hydroxy-2',5-dimethoxy-Z-naphthanilide3-hydroxy-2-naphth-o-toluidide 3-hydroxy-2-naphth-5-methyl-o-anisidide3-hydroxy-2-naphth-5-chloro-o-toluidide 3-hydroxy-2-naphth-2,4-xylidide3-hydroxy-2-naphth-o-anisidide 3-hydroxy-N-( l-napthyl)-2-naphthamide3-hydroxy-2-anthra-o-toluidide2-hydroxy-4-chloro-3-carbazolecarboxyarylide bisacetoacetbenzidide N-(l-naphthyl)acetoacetamide acetoacet-4'-chloro-2',5-dimethyoxyanilidel-(2,5-dimethoxyphenyl)-3-methyl-5-pyrazolonel-(Z-nitrophenylazo)-4-amino-6-hydroxynaphthalene6-(5-chloro-2-hydroxyphenylazo)resorcinol, copper salt The solution ofthe instant invention may then be padded on a cellulosic material suchas cotton, paper, cotton polyester mixed fiber, etc., or if the solutionhas been thickened to printing consistency, the material is thenprinted. The color is developed by exposing the padded fiber to heatsuch as superheated steam at 400 F. or dry heat for up to 3 minutes ashigh as 425 F. or by aging in neutral steam for 1-2 minutes.

It is noted that by employing the primary amine of the instant inventionin the neutral dyeing of azoic colors, one obtains improved coupling ofthe diazoamino compound and furthermore one obtains an improvedsplitting of the diazo compound especially if said diazo compound is ofthe slow" splitting" type than with prior art processes when the steamis employed.

In addition to the oxygen-containing primary amine and preferably asulfonated long chain carboxylic acid, one may also incorporate into thecomposition of the instant invention antifoam agents to control thefoaming thereof. Any commercially available antifoaming agents may beemployed in an amount which is effective for the control of foamformation. One type of antifoam agent which may be employed is of thesilicone type, such as DC antifoam (Dow Corning).

The present invention will now be described by reference to thefollowing specific examples. Such examples are presented for purposes ofillustration only, and the present invention is in no way to be deemedas limited thereto.

EXAMPLE 1 The following azoic solution was prepared:

Parts 3-hydroxy-2naphth-o-phenetidide 17;0 D iethylene glycol 5.0Dielhylene glycol ethyl ether 10.0 Methoxypropylamine 35.0 Acetylenicglycol 2,4.7,9-tetramethyl-5-decyne-4,7-

dial in ethylene glycol solution 1.0 Water 17.0 5-chloro-o-loluidinediazo stabilized with sarcosine (81%eonc.) 15.0

EXAMPLE 2 The following azoic solution was prepared:

Parts 3-hydroxy-Z-naphth-o-phenetidide 17.0 Methoxypropylamine 35.0Acetylenic glycol 2,4,7,9-tetramethyl-5-decyne-4,7-

diol in ethylene glycol solution 1.0 Sodium hydroxide 40Be' 3.5 Water28.5 S-chloro-o-mluidine diazo stabilized with sarcosine (81% cone.)15.0

EXAMPLE 3 The following azoic solution was prepared:

Farts 3-hydroxy-Z-naphth-o-phenetidide 17.0 Diethylene glycol ethylether 15.0 Methoxypropylamine 35.0 Acelylenic glycol2,4.7,9-tetramethyl-Sdecyne-4J- dial in ethylene glycol solution 1.0Sodium hydroxide 40Be' 3.5 Water 9.5 S-chloro-o-toluidine diazostabilized with cyanamid (58% cone.) 19.0

In Examples 1 through 3 clear solutions were obtained with thecompositions employed.

EXAMPLE 4 EXAMPLE 5 The following azoic solution was prepared:

Parts 3-hydtoxy-2-naphth-o-toluidide 17.0

Diethylene glycol 5.0

Diethylene glycol ethyl ether 10.0

Methoxypropylamine 35.0 Acetylenic glycol2.4,7,9-tetramethyl-5-decyne-4,7-

diol in ethylene glycol solution 1.0

Water 1 1.0 5-chloro-o-to1uldine diazo stabilized with sarcosine(81%conc.) 21.0

EXAMPLE 6 The following azoic solution was prepared:

Parts 3 hydroxy-2-naphth-o-toluidide 17.0 Methoxypropylamine 35.0Acetylenlc glycol 2,4.7,9-tetramethyl-5-decyne-4,7-

dial in ethylene glycol solution 1.0 Sodium hydroxide 40Be' 1.0 Water25.0 5-chloro-otoluidine diuzo stabilized with surcosine (81%eonc.) 21.0

EXAMPLE 7 The following azoic'solution was prepared:

Parts 3-hydroxy-Zmaphtlro-toluidide 17.0 Methoxyptopylamine 35.0Acetylenlc glycol 2,4.7.9-tetramethyl-5-decyne-4,7-

diol in ethylene glycol solution 1.0 Sodium hydroxide 40Be' 1.0 Water25.0 S-chloro-n-toluidine diazo stabilized with cyunamid (58% cone.)21.0

In all three cases clear solutions were obtained, but when the exampleswere repeated substituting for the methoxypropylamine the commercialdeveloper diethylaminoethanol the solutions were not clear and containedsediment.

EXAMPLE 8 The following azoic solution was prepared:

Parts Bis(acetoucet)-o-tolidide 9.2 Diethylene glycol ethyl ether 20.0Methoxypropylamir e 5.0 Acetylenic glycol2.4,7,9-tetramethyl-5-decyne-4,7-

diol in ethylene glycol solution 1.0 Sodium hydroxide 40Be' 4.0 Water46.8 S-chloro-o-toluidine diuzo stabilized with sarcosine (81% cone.)14.0

The solution was clear, but when a similar solution was prepared whereindiethylaminoethanol was substituted for the methoxypropylamine thesolution contained solids.

EXAMPLE 9 The following azoic solution was prepared:

A clear red solution was produced. However, when the methoxypropylaminewas substituted by diethylethanolamine, solids were present in thesolution.

EXAMPLE 10 The following azoic solution was prepared:

Parts 3-hydroxy-Z-naphth-o-phenetidide l3.0 Methoxypropylamine 35.0Acetylenic glycol 2.4.7.9-tetramethyl-5-decyne-4,7-

diol in ethylene glycol solution l.0 Diethylenc glycol ethyl ether 20.0Sodium hydroxide 40Be' 2.0 Water 56.0 N.N.-trimethylmethanilide.diazotized and stabilized N-methyl-S-sulfoanthranilic acid (78% conc.)23.0

This solution was clear, but a solution prepared whereindiethylaminoethanol was substituted for the methoxypropylamine containedsolids.

EXAMPLE ll The following azoic solution was prepared:

Parts 3-hydroxy-Z-naphth-o-anisidide l5l0 Methoxypropylamine 35.0Acetylenic glycol 2.4,7,9-tetramethyl-5-decyne- 4,7-

diol in ethylene glycol solution l.0 Diethylene glycol ethyl ether 10.0Sodium hydroxide 40Be' 2.0 Water $7.0 4-cyano-2,5Dimethoxyaniline,diazotized and stabilized with N-methyl-S-sulfoanthranilic acid (70%conc.) 30.0

A clear solution was produced, but when a solution was produced whereinthe methoxypropylamine was substituted by diethylethanolamine solidswere present in the solution.

EXAMPLE 12 The following azoic solution was prepared:

Parts 3-hydroxy-Z-naphthanilide l l.0

Methoxypropylamine 35.0 Acetylenic glycol 2,4,79-tetramethyl-5-decyne-4,7-

diol in ethylene glycol solution l.0

Sodium hydroxide 40Be L Water 422 Dianisidine. tetrazotized andstabilized with methyltaurine. (87% cone.) 9.8

This solution was clear, but a solution made in similar manner, onlysubstituting diethylaminoethanol for the methoxypropylamine, containedsolids.

EXAMPLE l3 The following azoic solution was prepared:

Parts S-amino-8-(phcnylozo)-2-nuphthol 7.0 Methoxypropylamine l5.0l-methyLZ-pyrtolidone 8.0 Thiodiglycol 8.0

Acetylenic glycol 2 4.7,9-tetram ethyl-S-decyne-4,7-

diol in ethylene glycol solution l.0 Sodium hydroxide 40Be' 1.0 Water47.0

Dianisidine. tetrazotized and stabilized with methyltaurine (87% cone.)[3.0

However, when the methox- A clear solution was produced.diethylethanolamine was substituted for ypropylamine the solutioncontained solids.

EXAMPLE 14 A composition was prepared comprising:

Urea Polygum 260 (5 (thickener) Polyvlnylpyrro done (K30)-30% aqueoussolution.. 3-hydroxy-2-naphth-o-phenetldlde (17 parts). Dlethyleneglycol (6 parts) Diethylene glycol ethyl ether (10 parts) 10Methoxypropylamlne (35 parts) Acetylenlc glycol2,4,7,9-tctramethyl-6-decyne-4,7-dlol in ethylene g ycol solution (1part). Water (17 parts) 5-chloro-o-toluldlne diazo stabilized withsarcoslno (81% wcgnccntrate) parts) a er The resultant paste was printedon three swatches of cotton cloth and the prints were dried anddeveloped. One swatch was dried and developed by treatment with dry heatfor three 20 minutes at 350 F. The second swatch was aged in neutralsteam at atmospheric pressure for 1 minute. The third swatch was treatedwith superheated steam at 400 F. for 2 minutes. In all cases full colordeveloped. The development was attributed to the evaporation of thevolatile amine as no fixed alkali was present in the composition of thisexample.

EXAMPLE IS A composition was prepared comprising:

Urea Polygum 260 (5 (thickener Polyvlnylpyrro idone 25 partsmethoxypropylamine.

20 parts diethylene gly ol.

3 5 25 parts a-suliostearic acid 3-hydroxy-2-na hth-ophenetidide (17parts Methoxypropy amine parts) Acetylenlc glycol2,4,7,9-tetramethyl-5-decyne-4,7-diol in ethyleneg ycol solution (1part) Sodium hy roxide Be (3.5 parts) Water (28.5 parts) 40b-chloro-o-toluidine diazo stabilized with sarcosine (81% Wcmcentrate)(15.0 parts) a er The resultant paste was printed on three swatches ofcotton cloth and the prints were then dried and developed by treatingthe first swatch with dry heat for 3 minutes at 350 F. The second swatchwas aged in neutral steam at atmospheric pressure for 1 minute. Thethird swatch was treated with superheated steam at 400 F. for 2 minutes.In all cases full color developed.

EXAMPLE 16 A composition was prepared comprising:

The resultant paste was printed on three swatches of cotton cloth andthe prints were then dried and developed by treating the first swatchwith dry heat for 3 minutes at 350 F. The second swatch was aged inneutral steam at atmospheric pressure for l minute. The third swatch wastreated with superheated steam at 400 F. for 2 minutes. In all casesfull color developed.

EXAMPLE 17 A composition was prepared comprising:

Diethylene glycoiethyl ether (10 parts). Methoxypropylamine (35 parts)Acetylenic glycol 2,4,7,9-tetramethyl-5-decyne-4,7-

ethylene glycol solution (1 part) Water (11 parts) fi-chloro-o-toluidinediazo concentrate) (21 parts). Water EXAMPLES 20-26 The compositions ofexamples I throughowere prepared with the exception thatdiethylethanolamine wassubstituted for the methoxypropylamine employedtherein. As previously stated, the solutions contained solids and weretherefore filtered. The filtered solutions were then thickenedtoprinting 1 consistency and printed on cotton cloth samples, dried anddeveloped in the manner employedin examples 14-19. in all cases thecolorwhich developed 'wasdull, indicating that full The resultant pastewasprinted on three swatches of cotton cloth and the prints weredriedand developed. One swatch was dried and developed by treatment withdry heat for 3 minutes at 350 F. The second swatch was aged inneutralsteam at atmospheric pressure for 1 minute. The third swatch was treatedwith superheated steam at 400 F. for 2 minutes. in all cases full colordeveloped. The developmentwas attributed to the evaporation of thevolatile amine asno fixed al-. kali was present in the composition ofthis example.

EXAMPLE l8 A composition was prepared comprising:

The resultant paste was printed on three swatches ofcotton cloth and theprints were then dried and developed by treating the first swatch withdry heat for} minutes at 350 F. The second swatch was aged in neutralsteam at atmospheric pressure for 1 minute. The third swatch was treatedwith superheated steam at 400 F. for 2 minutes. In all cases full colordeveloped.

EXAMPLE 19 A composition was prepared comprising;

The resultant paste was printed on three swatches of cotton cloth andthe prints were then dried anddeveioped by treating the first swatchwith dry heat for 3 minutes at 350 F. The second swatch was aged inneutral steam at atmospheric pressure for 1 minute. The third swatchwastreated with superheated steam at 400 F. for 2 minutes. In all casesfull color developed.

20 r 3-hydroxy-2-na hth-o-phenet colorvalue was not obtained.

EXAMPLE 27 A composition comprising the followingwasprepared:

Parts Polygum 260 (5%) thick Polyvinyl pyrrolidone.

D Methox ropy mine (35 parts) Acetyle c glycol 2,47,9-tetramethyl-5-decyne-4, diol ethylene glycol solution (1 part)Sodium hydroxide 40 B. (3.5 parts) Water (28.5 parts)5-chloro-o-toluidine .diazo stabilized with sarcosine (81% concentate)parts)- eveloper:

Methoxypropylene (25 parts) Diethylene glycol parts). a-Suliostearicacid parts) to which. was. added 4 parts of a dye having the formula:

EXAMPLE 2s A The following composition was prepared:

Parts Ur ea i fi i lid 0 y ny yrro one Azoic dove oper comprising:

Methoxypropylene' (25 parts) Diethylene ly'cotm parts) a-Suliostear 0acid (25 parts) Kelgin (1:100, a hifihlyrefined algin product)...a-hydroxy-2 napht -o -phenetiddo (17 parts) Diethylene glycol (llperts)Diethylene glycolethyl ether (10 parts) ropyla'mine parts) Aeetylen cglycol 2,4 7,Q-tetromethyiodecyne-4J-dlol in ethylene glycol solution (1part) Water (17 parts) 5-ehloro-o-to1uidine diazo stabilized withsax-cosine (81% wcttmcentrate) (15 parts) a on...

EXAMPLE 29 The compositionof example 28 was prepared, to which was added8 parts of adye having a formula:

pom n; ONH-O j N=N CH3 and 3 parts dispersed dye from5-chloro-o-toluidine diazotized and coupled with3-hydroxy-2naphtho-o-toluidide. This composition was padded on to apolyester cotton (65:35) swatch and cured at 425 F. for 1% minutes. Theswatch developed full color and the fabric had good fastness to light,washing, dry-cleaning and sublimation.

EXAMPLE 30 The following composition was prepared:

The product was padded on to a cotton material and and developed as inexamples 28 and 29. In all cases solid shades having full color valuewere produced.

EXAMPLE 31 The composition of example 30 was prepared, to which wasadded 8 parts of a dispersed dye from 4'-aminobenzanilide diazotized andcoupled with paracresol in place of 8 parts of water. The solution waspadded on to polyester-cotton (65:35) material and developed as inexample 30. Solid shades having full color value were produced.

EXAM PLE 3 2 A composition comprising the following was prepared:

Parts Urea 30.0 Water 30.0 Polyvinylpyrrolidone 2.0 Azoic developercomprising:

25 parts methoxypropylamine parts diethylene glycol 3.0 partsa-sulfostearic acid Kelgin (1:100) 20.0 Product of Example 8 10.0Dispersed dyc from 4-an1inobenzanilidc diazotized and coupled withparacresol 8.0 Water 30.0

The product was padded on to polyester-cotton (65:35) material anddeveloped as in Example 30. Solid shades having full color value wereproduced.

EXAMPLES 33-37 Solution of Example:

These pastes were printed on cotton cloth, dried developed in the manner$55,11 ,165 14-19. In all cases full color developed.

EXAMPLE 38 An azoic solution was compounded according to the formulationof Example 2 with the exception that ethoxyethylamine was used insteadof methoxypropylamine. The resulting solution was compounded into aprinting paste in the manner of examples 14-19, printed on cotton, driedand developed with dry heat for 3 minutes at 350 F. As in the previousexamples, full color developed.

EXAMPLE 39 An azoic solution was compounded according to the formulationof example 2, with the exception that methoxybutylamine replacedmethoxypropylamine therein. The resulting solution was compounded into aprinting paste in the manner of examples 14-19, printed on cotton, driedand developed with dry heat for 3 minutes at 350 F. As in the previousexamples, full color developed.

EXAMPLE 40 An azoic solution was prepared wherein a-sulfolauric acidreplaced a-sulfostearic acid in equivalent amounts. Example 15 was thenrepeated with the substitution of the azoic solution of this example.Full color value resulted on development in the manner of example 39.

EXAMPLE 41 An azoic solution was prepared wherein a-sulfopalmitic acidreplaced a-sulfostearic acid in equivalent amounts. Example 15 was thenrepeated with the substitution of the azoic solution of this example.Full color value resulted on development in the manner of example 40.

a-sulfostearic acid (25 parts) a. to which 10 parts of the product ofexample 8 (fast splitting) was added.

b. to which 10 parts of the product of Example 8 with 5-chloro-o-toluidine diazo stabilized with cyanamide (fast splitting) wassubstituted for the sarcosine stabilized diazo compound was added. (slowsplitting) c. to which 10 parts of the product of example 3 was added.

to which 10 parts of the product of example 4 was added.

e. to which 10 parts l-(p-aminophenyl)-3-methyl-5- pyrazolone reactedwith nickel phthalocyanine sulfonyl chloride (coupler) and5-chloro-o-toluidine diazo stabilized with cyanamid (diazo) (fastsplitting) was added.

f. to which 10 parts of a solution comprising 4'-chlor0-2-hydroxy3-carboxanilide (coupler) and S-chloro-otoluidine diazostabilized with cyanamid (azo) (fast splitting) was added.

g. to which 10 parts of a solution comprising 4'-chloro-2-hydroxy-3-carboxanilide (coupler) and p-toluidine diazo stabilized withsarcosine was added.

The The volume of each was adjusted to 133 cc. with hot water. Filterpaper, and also bond paper were passed through these solutions at about75-90 F. The papers were then exposed to a temperature of about C. Thefast splitting types developed full color on drying whereas the slowsplitting types required about one-half hour at this temperature todevelop full color. Under conditions of paper manufacture where thetemperature is higher, the colors can be expected to develop fully inless time.

A composition comprising the following was prepared:

Parts I. Polygum 260(17) 45 Ureu 20 Polyvinyl pyrrolidone (K30) 30%aqueous solution 2 a. To the above composition was added parts of thecom: position comprising Parts Z-hydroxy-Il-carbazolecarbox-p-chloroanilide 7.5 J-methoxypropylamine 40 Ethoxyethanol 5Caustic sodu flakes 2 Water 45.5

and 1.5 parts of p-toluidine diazo stabilized with cyanamid.

Parts Z-hydroxy-2'.5'-dlrnethoxy-3 -dibenzofuranecarboxanilide 7.5B-methoxypropylamine 40 Ethoxyethanol 5 Caustic soda flakes 2 Water 45.5

and 1.4 parts of S-chloro-o-toluidine diazostabilized with cyanamide.

d. The composition of (c) was preparedwith the exception that 2.5 partsof S-nitro-o-anisidine diazo stabilized was sub:

' stituted for 1.4 parts of S-chloro-o-toluidine diazo stabilized wasadded to the compositions of said examples. The pastes with cyanamide e.To the above composition (1) was added 10 partsof the compositioncomprising Par 2-hydroxy-5'-methyl-3 -dibenzofuranecarbox-oanisidide 7.5J-Methoxypropylamine 40 Ethoxyethunol 5 Caustic soda flakes 2 Water 45.5

and 1.4 parts of S-chlot'o-mtoluidine diazo stabilized with cyanamide.

f. The compositionof (e) was prepared with the exception that 1.5 partsof p-Toluidine diazo stabilized with cyanamide was substituted for 1.4parts of 5-chlor-o-toluidine diazo sta-- Parts Z-hydroxy-ll-benzo[a]carbazole- B-carbox-p-anisidide 7.5 3-Methoxypropylamine 40Ethoxyethanol 5 Caustic soda flakes Z a Water 45.5

and 2.4 parts of5-Nitro-o-anisidine diazo stabilized.

The resultant pastes were printed on cotton swatches and the prints werethen treated and developed for 1 minutes at 425 F. in all cases, fullcolor developed.

EXAMPLE 57 Examples 14 through l9 were repeated with the exception that2.5 parts of a composition comprising;

Parts DC antiiosm agents 30 Sodium sulfate 970 were printed in themanner described in examples 14 through 19 and prints made therefromdeveloped full color value. ln

addition, the foaming properties-of the composition were inhibited.

What is claimed is:

1. In the method of neutral steam developing of azoic dyes. theimprovement which comprises applying to the material to be dyed adeveloper composition comprising coupling component, diazoaminocompound, an oxygen-containing primary amine having the formula:

., -oazwm.

whereinR represents an alkyl radicalhaving from l- 4 carbon atoms, nrepresents an integer of from 2-4, and the totalcarbon atoms in themolecule range from 3-5.

2. in the method of neutralsteam developing of azoic dyes. theimprovement which comprises applying to the material to be dyed-adeveloper composition comprising coupling component, diazoaminocompound, an-oxygen-containing primary amine having the formula:

wherein R represents an alkylradical having from 14 carbon atoms, nrepresents an integer of from 2-4, and the total carbonatoms in themolecule range from 3-5,.and a sulfonated. long-chain monocarboxylicacid.

3. The method of claim 1 wherein the oxygen-containing primary amineismethoxypropylamine.

4. The method. of claim 2 wherein the oxygen-containing primary amineis-inethoxypropylamine.

5. The method of claim 2 wherein the sulfonatedlong-cham monocarboxylicacid has from l2-l 8 carbon atoms.

6.- The method of claim 2 wherein the sulfonated long-chainmonocarboxylic acid is a-sulfostearic acid.

7. The method of claim 2 wherein the sulfonated long-chainmonocarboxylic acid isa-sulfolauric acid.

8. The method of claim 2 wherein the sulfonated long-chainmonocarboxylic acid isa-sulfopalmitic acid;

9. An azoic dye composition comprising, coupling component, diazoaminocompound, and an oxygen-containing primary amine having the formula: 3

z)" 2 wherein R represents an alkyl radical having from l4 carbon atoms.n represents an integer of from 2-4. and the totul curbon atoms in themolecule range from 35.

ill. The composition of claim 9 wherein the oxygen-containing primaryamine is methoxypropylamine.

fonated long-chain monocarboxylic acid has from 12-18 car- 'bon atoms.

14. The composition of claim 11 wherein the sulfonated long-chainmonocarboxylic acid is a-sulfostearic acid.

15. The composition according to claim 11 wherein the sulfonatedlong-chain monocarboxylic acid is a-sulfolauric acid.

16. The composition according to claim ll wherein the sulfonatedlong-chain monocarboxylic acid is zx-sulfopalmitic acid.

2. In the method of neutral steam developing of azoic dyes, theimprovement which comprises applying to the material to be dyed adeveloper composition comprising coupling component, diazoaminocompound, an oxygen-containing primary amine having the formula:R-O-(CH2)n-NH2 wherein R represents an alkyl radical having from 1-4carbon atoms, n represents an integer of from 2-4, and the total carbonatoms in the molecule range from 3-5, and a sulfonated long-chainmonocarboxylic acid.
 3. The method of claim 1 wherein theoxygen-containing primary amine is methoxypropylamine.
 4. The method ofclaim 2 wherein the oxygen-containing primary amine ismethoxypropylamine.
 5. The method of claim 2 wherein the sulfonatedlong-chain monocarboxylic acid has from 12-18 carbon atoms.
 6. Themethod of claim 2 wherein the sulfonated long-chain monocarboxylic acidis Alpha -sulfostearic acid.
 7. The method of claim 2 wherein thesulfonated long-chain monocarboxylic acid is Alpha -sulfolauric acid. 8.The method of claim 2 wherein the sulfonated long-chain monocarboxylicacid is Alpha -sulfopalmitic acid.
 9. An azoic dye compositioncomprising coupling component, diazoamino compound, and anoxygen-containing primary amine having the formula: R-O-(CH2)n-NH2wherein R represents an alkyl radical having from 1-4 carbon atoms, nrepresents an integer of from 2-4, and the total carbon atoms in themolecule range from 3-5.
 10. The composition of claim 9 wherein theoxygen-containing primary amine is methoxypropylamine.
 11. An azoic dyecomposition comprising coupling component, diazoamine compound, and anoxygen-containing primary amine having the formula: R-O-(CH2)n-NH2wherein R represents an alkyl radical having from 1-4 carbon atoms, nrepresents an integer of from 2-4, and there are between three and fivecarbon atoms in the molecule, and a sulfonated long-chain monocarboxylicacid.
 12. The composition of claim 11 wherein the oxygen-containingprimary amine is methoxypropylamine.
 13. The composition according toclaim 11 wherein the sulfonated long-chain monocarboxylic acid has from12-18 carbon atoms.
 14. The composition of claim 11 wherein thesulfonated long-chain monocarboxylic acid is Alpha -sulfostearic acid.15. The composition according to claim 11 wherein the sulfonatedlong-chain monocarboxylic acid is Alpha -sulfolauric acid.
 16. Thecomposition according to claim 11 wherein the sulfonated long-chainmonocarboxylic acid is Alpha -sulfopalmitic acid.